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Mesoporous carbons supported non-noble metal Fe–N X electrocatalysts for PEM fuel cell oxygen reduction reaction

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Abstract

Three types of iron–nitrogen-containing non-noble metal catalysts, supported on an ultrasonic spray pyrolysis mesoporous carbon (USPMC), a hollow core mesoporous shell carbon (HCMSC), and a standard carbon (Ketjen Black CJ600, KB), respectively, are synthesized using a wet-impregnation method. The morphologies and structure as well as composition of the synthesized carbon supports and their corresponding supported Fe–N X catalysts (namely Fe–N X /USPMC, Fe–N X /HCMSC, and Fe–N X /KB, respectively) are physically characterized using EDX, SEM, FESEM, and BET analysis, respectively. The catalytic activities of these three electrocatalysts toward oxygen reduction reaction (ORR) are measured using rotating disk electrode technique in O2-saturated 0.5 M H2SO4 solution. The catalyzed ORR exchange current densities are also obtained using the Tafel method based on the measured data. Among these three electrocatalysts, Fe–N X /HCMSC can give the best ORR performance, which is correlated to its higher nitrogen, mesopore, and micropore contents, compared to the other electrocatalysts. It is rationalized that the performance improvement of these electrocatalysts may be achieved as long as an optimal relationship among mesopores, micropores, and even macropores for increasing both ORR kinetics and reactant gases accessibility to the active sites can be found.

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References

  1. Wu G, More KL, Johnston CM, Zelenay P (2011) High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332:443–447

    Article  CAS  Google Scholar 

  2. Specchia S, Francia C, Spinelli P (2011) Polymer electrolyte membrane fuel cells. In: Electrochemical technologies for energy storage and conversion, 1st edn. Wiley-VHC, Weinheim, pp 601–670

  3. Ohma A, Mashio T, Sato K, Iden H, Ono Y, Sakai K, Akizuki K, Takaichi S, Shinohara K (2011) Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan. Electrochim Acta 56:10832–10841

    Article  CAS  Google Scholar 

  4. The Department of Energy, Hydrogen and Fuel Cells Program Plan (2011) An integrated strategic plan for the research, development, and demonstration of hydrogen and fuel cell technologies. www.hydrogen.energy.gov/pdfs/program_plan2011.pdf. Accessed 12 July 2012

  5. Chen ZW, Waje M, Li WZ, Yan YS (2007) Supportless Pt and PtPd nanotubes as electrocatalysts for oxygen-reduction reactions. Angew Chem Int Ed 46:4060–4063

    Article  CAS  Google Scholar 

  6. Ramaswamy N, Arruda TM, Wen W, Hakim N, Saha M, Gullá A, Mukerjee S (2009) Enhanced activity and interfacial durability study of ultra low Pt based electrocatalysts prepared by ion beam assisted deposition (IBAD) method. Electrochim Acta 54:6756–6766

    Article  CAS  Google Scholar 

  7. Liao MJ, Wei ZD, Chen SG, Li L, Ji MB, Wang YQ (2010) Ultra low Pt-loading electrode prepared by displacement of electrodeposited Cu particles on a porous carbon electrode. Int J Hydrogen Energy 35:8071–8079

    Article  CAS  Google Scholar 

  8. Esmaeilifar A, Rowshanzamir S, Eikani MH, Ghazanfari E (2010) Synthesis methods of low-Pt-loading electrocatalysts for proton exchange membrane fuel cell systems. Energy 35:3941–3957

    Article  CAS  Google Scholar 

  9. Sebastián D, Lázaro MJ, Suelves I, Moliner R, Baglio V, Stassi A, Aricò AS (2012) The influence of carbon nanofiber support properties on the oxygen reduction behavior in proton conducting electrolyte-based direct methanol fuel cells. Int J Hydrogen Energy 37:6253–6260

    Article  Google Scholar 

  10. Zeng J, Francia C, Dumitrescu MA, Monteverde Videla AHA, Ijeri VS, Specchia S, Spinelli P (2012) Electrochemical performance of Pt-based catalysts supported on different ordered mesoporous carbons (Pt/OMCs) for oxygen reduction reaction. Ind Eng Chem Res 51:7500–7509

    Article  CAS  Google Scholar 

  11. Sebastián D, García Ruíz A, Suelves I, Moliner R, Lázaro MJ, Baglio V, Stassi A, Aricò AS (2012) Enhanced oxygen reduction activity and durability of Pt catalysts supported on carbon nanofibers. Appl Catal B: Environ 115–116:269–275

    Article  Google Scholar 

  12. Chen ZW, Higgins DC, Yu A, Zhang L, Zhang J (2011) A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ Sci 4:3167–3192

    Article  CAS  Google Scholar 

  13. Wang L, Zhang L, Zhang J (2011) Improved ORR activity of non-noble metal electrocatalysts by increasing ligand and metal ratio in synthetic complex. Electrochim Acta 56:5488–5492

    Article  CAS  Google Scholar 

  14. Oh HS, Kim H (2012) The role of transition metals in non-precious nitrogen-modified carbon-based electrocatalysts for oxygen reduction reaction. J Power Sources 212:220–225

    Article  CAS  Google Scholar 

  15. Lefèvre M, Proietti E, Jaouen F, Dodelet JP (2009) Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324:71–74

    Article  Google Scholar 

  16. Liu H, Song C, Tang Y, Zhang J, Zhang J (2007) High-surface-area CoTMPP/C synthesized by ultrasonic spray pyrolysis for PEM fuel cell electrocatalysts. Electrochim Acta 52:4532–4538

    Article  CAS  Google Scholar 

  17. Chen Z, Higgins DC, Chen ZW (2010) Electrocatalytic activity of nitrogen doped carbon nanotubes with different morphologies for oxygen reduction reaction. Electrochim Acta 55:4799–4804

    Article  CAS  Google Scholar 

  18. Chen Z, Higgins DC, Chen ZW (2010) Nitrogen doped carbon nanotubes and their impact on the oxygen reduction reaction in fuel cells. Carbon 48:3057–3065

    Article  CAS  Google Scholar 

  19. Choi J, Higgins DC, Chen ZW (2011) Highly durable graphene nanosheet supported iron catalyst for oxygen reduction reaction in PEM fuel cells. J Electrochem Soc 159:B87–B90

    Article  Google Scholar 

  20. Higgins DC, Chen Z, Chen ZW (2011) Nitrogen doped carbon nanotubes synthesized from aliphatic diamines for oxygen reduction reaction. Electrochim Acta 56:1570–1575

    Article  CAS  Google Scholar 

  21. Collman JP, Marrocco M, Denisevich P, Koval C, Anson FC (1979) Potent catalysis of the electroreduction of oxygen to water by dicobalt porphyrin dimers adsorbed on graphite electrodes. J Electroanal Chem Interfacial Electrochem 101:117–122

    Article  CAS  Google Scholar 

  22. Collman JP, Denisevich P, Konai Y, Marrocco M, Koval C, Anson FC (1980) Electrode catalysis of the four-electron reduction of oxygen to water by dicobalt face-to-face porphyrins. J Am Chem Soc 102:6027–6036

    Article  CAS  Google Scholar 

  23. Liu HY, Weaver MJ, Wang CB, Chang CK (1983) Dependence of electrocatalysis for oxygen reduction by adsorbed dicobalt cofacial porphyrins upon catalyst structure. J Electroanal Chem Interfacial Electrochem 145:439–447

    Article  CAS  Google Scholar 

  24. Yeager EB (1984) Electrocatalysts for O2 reduction. Electrochim Acta 29:1527–1537

    Article  CAS  Google Scholar 

  25. Scherson D, Tanaka AA, Gupta SL, Tryk D, Fierro C, Holze R, Yeager EB (1986) Transition metal macrocycles supported on high area carbon: pyrolysis—mass spectrometry studies. Electrochim Acta 31:1247–1258

    Article  CAS  Google Scholar 

  26. Morcos I, Yeager EB (1970) Kinetic studies of the oxygen–peroxide couple on pyrolytic graphite. Electrochim Acta 15:953–975

    Article  CAS  Google Scholar 

  27. Jaouen F, Lefèvre M, Dodelet JP, Cai M (2006) Heat-treated Fe/N/C catalysts for O2 electroreduction: are active sites hosted in micropores? J Phys Chem B 110:5553–5558

    Article  CAS  Google Scholar 

  28. Jaouen F, Proietti E, Lefèvre M, Chenitz R, Dodelet JP, Wu G, Chung HT, Johnston CM, Zelenay P (2011) Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells. Energy Environ Sci 4:114–130

    Article  CAS  Google Scholar 

  29. Velázquez-Palenzuela A, Zhang L, Wang L, Cabot PL, Brillas E, Tsay K, Zhang J (2011) Fe–Nx/C electrocatalysts synthesized by pyrolysis of Fe(II)–2,3,5,6-tetra(2-pyridyl)pyrazine complex for PEM fuel cell oxygen reduction reaction. Electrochim Acta 56:4744–4752

    Article  Google Scholar 

  30. Li S, Zhang L, Liu H, Pan M, Zan L, Zhang J (2010) Heat-treated cobalt–tripyridyl triazine (Co–TPTZ) electrocatalysts for oxygen reduction reaction in acidic medium. Electrochim Acta 55:4403–4411

    Article  CAS  Google Scholar 

  31. Liu H, Zhang J (2009) Controllable synthesis of porous carbon spheres, and electrochemical applications thereof. Patent WO2009/149540 A1

  32. Zeng J, Francia C, Gerbaldi C, Dumitrescu MA, Specchia S, Spinelli P (2012) Smart synthesis of hollow core mesoporous shell carbons (HCMSC) as effective catalyst supports for methanol oxidation and oxygen reduction reactions. J Solid State Electrochem 16:3087–3096

    Article  CAS  Google Scholar 

  33. Büchel G, Unger KK, Matsumoto A, Tsutsumi K (1998) A novel pathway for synthesis of submicrometer-size solid core/mesoporous shell silica spheres. Adv Mater 10:1036–1038

    Article  Google Scholar 

  34. Jun S, Joo SH, Ryoo R, Kruk M, Jaroniec M, Liu Z, Ohsuna T, Terasaki O (2000) Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure. J Am Chem Soc 122:10712–10713

    Article  CAS  Google Scholar 

  35. Kruk M, Jaroniec M (2001) Gas adsorption of ordered organic-inorganic nanocomposite materials. Chem Mater 13:3169–3183

    Article  CAS  Google Scholar 

  36. Jaroniec M, Solovyov LA (2006) Improvement of the Kruk–Jaroniec–Sayari method for pore size analysis of ordered silicas with cylindrical mesopores. Langmuir 22:6757–6760

    Article  CAS  Google Scholar 

  37. Liu LiX, Ganesan P, Popov BN (2010) Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells. Electrochim Acta 55:2853–2858

    Article  CAS  Google Scholar 

  38. Aricò AS, Antonucci V, Minutoli M, Giordano N (1989) The influence of functional groups on the surface acid–base characteristics of carbon blacks. Carbon 27:337–347

    Article  Google Scholar 

  39. Zhu M, Weber CJ, Yang KM, Starke U, Kern K, Bittner AM (2008) Chemical and electrochemical ageing of carbon materials used in supercapacitor electrodes. Carbon 46:1829–1840

    Article  CAS  Google Scholar 

  40. Shrestha S, Mustain WE (2010) Properties of nitrogen-functionalized ordered mesoporous carbon prepared using polypyrrole precursor. J Electrochem Soc 157:B1665–B1672

    Article  CAS  Google Scholar 

  41. Subramanian NP, Kumaraguru SP, Colon-Mercado H, Kim H, Popov BN, Black T, Chen DA (2006) Studies on Co-based catalysts supported on modified carbon substrates for PEMFC cathodes. J Power Source 157:56–63

    Article  CAS  Google Scholar 

  42. Shao Y, Zhang S, Engelhard MH, Li G, Shao G, Wang Y, Liu J, Aksay IA, Lin Y (2010) Nitrogen-doped graphene and its electrochemical applications. J Mater Chem 20:7491–7496

    Article  CAS  Google Scholar 

  43. Kamiya K, Hashimoto K, Nakanishi S (2012) Instantaneous one-pot synthesis of Fe–N-modified graphene as an efficient electrocatalyst for the oxygen reduction reaction in acidic solutions. Chem Commun 48:10213–10215

    Article  CAS  Google Scholar 

  44. Wang H, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2:781–794

    Article  CAS  Google Scholar 

  45. Gasteiger HA, Kocha SS, Sompalli B, Wagner FT (2005) Activity benchmarks and requirements for Pt, Pt-alloys, and non-Pt oxygen reduction catalysts for PEMFC. Appl Catal B Environ 56:9–35

    Article  CAS  Google Scholar 

  46. Matter PH, Zhang L, Ozkan US (2006) The role of nano-structure in nitrogen-containing carbon catalysts for the oxygen reduction reaction. J Catal 239:83–96

    Article  CAS  Google Scholar 

  47. Arrigo R, Havecker M, Schlogl R, Su DS (2008) Dynamic surface rearrangement and thermal stability of nitrogen functional groups on carbon nanotubes. Chem Commun 40:4891–4893

    Article  Google Scholar 

  48. Niwa H, Horiba K, Harada Y, Oshima M, Ikeda T, Terakura K, Ozaki J, Miyata S (2009) Instantaneous one pot synthesis of Fe–N-modified graphene as an efficient electrocatalyst for the oxygen reduction reaction in acidic solutions. J Power Sources 187:93–97

    Article  CAS  Google Scholar 

  49. Liu H, Shi Z, Zhang J, Zhang L, Zhang J (2009) Ultrasonic spray pyrolyzed iron-polypyrrole mesoporous spheres for fuel cell oxygen reduction electrocatalysts. J Mater Chem 19:468–470

    Article  CAS  Google Scholar 

  50. van Veen JAR, Colijn HA, van Baar JF (1988) On the effect of a heat treatment on the structure of carbon-supported metalloporphyrins and phthalocyanines. Electrochim Acta 33:801–804

    Article  Google Scholar 

  51. Bouwkamp-Wijnoltz AL, Visscher W, van Veen JAR, Tang SC (1999) Electrochemical reduction of oxygen: an alternative method to prepare active CoN4 catalysts. Electrochim Acta 45:379–386

    Article  CAS  Google Scholar 

  52. Liang C, Li Z, Dai S (2008) Mesoporous carbon materials: synthesis and modification. Angew Chemie Int Ed 47:3696–3717

    Article  CAS  Google Scholar 

  53. Marcotte S, Villers D, Guillet N, Roué L, Dodelet JP (2004) Electroreduction of oxygen on Co-based catalysts: determination of the parameters affecting the two-electron transfer reaction in an acid medium. Electrochim Acta 50:179–188

    Article  CAS  Google Scholar 

  54. Song C, Zhang J (2008) Electrocatalytic oxygen reduction reaction. In: PEM fuel cell electrocatalysts and catalyst layers, fundamental and applications, 1st edn. Springer, London, pp 89–134

  55. Stassi A, D’Urso C, Baglio V, Di Blasi A, Antonucci V, Aricò AS, Castro Luna AM, Bonesi A, Triaca WE (2006) Electrocatalytic behaviour for oxygen reduction reaction of small nanostructured crystalline bimetallic Pt–M supported catalysts. J Appl Electrochem 36:1143–1149

    Article  CAS  Google Scholar 

  56. Wang P, Ma Z, Zhao Z, Jia L (2007) Oxygen reduction on the electrocatalysts based on pyrolyzed non-noble metal/poly-o-phenylenediamine/carbon black composites: new insight into the active sites. J Electroanal Chem 611:87–95

    Article  CAS  Google Scholar 

  57. Qiao J, Lin R, Li B, Ma J, Liu J (2010) Kinetics and electrocatalytic activity of nanostructured Ir–V/C for oxygen reduction reaction. Electrochim Acta 55:8490–8497

    Article  CAS  Google Scholar 

  58. Zhang H-J, Yuan X, Sun L, Zeng X, Jiang Q-Z, Shao Z, Ma Z-F (2010) Pyrolyzed CoN4-chelate as an electrocatalyst for oxygen reduction reaction in acid media. Int J Hydrogen Energy 35:2900–2903

    Article  CAS  Google Scholar 

  59. Pei K, Banham D, Feng F, Fürstenhaupt T, Ye S, Birss V (2010) Oxygen reduction activity dependence on the mesoporous structure of imprinted carbon supports. Electrochem Commun 12:1666–1669

    Article  CAS  Google Scholar 

  60. Lai L, Potts JR, Zhan D, Wang L, Kok Poh C, Tang C, Gong H, Shen Z, Lin J, Ruoff RS (2012) Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ Sci 5:7936–7942

    Article  CAS  Google Scholar 

  61. Coutanceau C, Croissant MJ, Napporn T, Lamy C (2000) Electrocatalytic reduction of dioxygen at platinum particles dispersed in a polyaniline film. Electrochim Acta 46:579–588

    Article  CAS  Google Scholar 

  62. Kapałka A, Foti G, Comninellis C (2008) Determination of the Tafel slope for oxygen evolution on boron-doped diamond electrodes. Electrochem Commun 10:607–610

    Article  Google Scholar 

  63. Li S, Zhang L, Kim J, Pan M, Shi Z, Zhang J (2010) Synthesis of carbon-supported binary FeCo–N non-noble metal electrocatalysts for the oxygen reduction reaction. Electrochim Acta 55:7346–7353

    Article  CAS  Google Scholar 

  64. Wang L, Zhang L, Zhang J (2011) Optimizing catalyst loading in non-noble metal electrocatalyst layer to improve oxygen reduction reaction activity. Electrochem Commun 13:447–449

    Article  CAS  Google Scholar 

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Acknowledgments

Dr Edvige Celasco and Mr Mauro Raimondo from Politecnico di Torino are gratefully acknowledged for SEM/XPS analysis. The authors express their gratitude and recognition to Dr Brian McLernon from National Research Council of Canada and Prof. Paolo Spinelli from Politecnico di Torino for the valuable and fruitful discussions.

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Authors and Affiliations

  1. Politecnico di Torino, Department of Applied Science and Technology, Corso Duca degli Abruzzi 24, 10129, Turin, Italy

    Alessandro H. A. Monteverde Videla, Juqin Zeng, Carlotta Francia & Stefania Specchia

  2. National Research Council, Energy, Mining & Environment Portfolio, Government of Canada, 4250 Wesbrook Mall, Vancouver, BC, V6T 1W5, Canada

    Alessandro H. A. Monteverde Videla, Lei Zhang, Jenny Kim & Jiujun Zhang

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  1. Alessandro H. A. Monteverde Videla
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  2. Lei Zhang
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  3. Jenny Kim
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  4. Juqin Zeng
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  5. Carlotta Francia
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  6. Jiujun Zhang
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  7. Stefania Specchia
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Correspondence to Stefania Specchia.

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Monteverde Videla, A.H.A., Zhang, L., Kim, J. et al. Mesoporous carbons supported non-noble metal Fe–N X electrocatalysts for PEM fuel cell oxygen reduction reaction. J Appl Electrochem 43, 159–169 (2013). https://doi.org/10.1007/s10800-012-0497-y

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